EP1079962A1 - Dekorinnenteile für autos mit in der form beschichteter, integrierter elastomerabdeckung aus aromatischem polyurethan und verfahren zur herstellung derselben - Google Patents
Dekorinnenteile für autos mit in der form beschichteter, integrierter elastomerabdeckung aus aromatischem polyurethan und verfahren zur herstellung derselbenInfo
- Publication number
- EP1079962A1 EP1079962A1 EP99920485A EP99920485A EP1079962A1 EP 1079962 A1 EP1079962 A1 EP 1079962A1 EP 99920485 A EP99920485 A EP 99920485A EP 99920485 A EP99920485 A EP 99920485A EP 1079962 A1 EP1079962 A1 EP 1079962A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- outer layer
- mold surface
- mold
- layered composite
- diisocyanate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 46
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 46
- 239000004814 polyurethane Substances 0.000 title claims abstract description 46
- 230000008569 process Effects 0.000 title claims abstract description 33
- 125000003118 aryl group Chemical group 0.000 title claims description 29
- 229920001971 elastomer Polymers 0.000 title description 15
- 239000000806 elastomer Substances 0.000 title description 15
- 239000000203 mixture Substances 0.000 claims abstract description 83
- 239000000758 substrate Substances 0.000 claims abstract description 42
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims abstract description 34
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims abstract description 34
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 26
- 230000003014 reinforcing effect Effects 0.000 claims abstract description 26
- 230000001413 cellular effect Effects 0.000 claims abstract description 21
- 239000000126 substance Substances 0.000 claims abstract description 19
- 239000006260 foam Substances 0.000 claims abstract description 18
- 229920003225 polyurethane elastomer Polymers 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000002131 composite material Substances 0.000 claims description 71
- 229920005862 polyol Polymers 0.000 claims description 30
- 150000003077 polyols Chemical class 0.000 claims description 30
- 239000005056 polyisocyanate Substances 0.000 claims description 26
- 229920001228 polyisocyanate Polymers 0.000 claims description 26
- 125000000524 functional group Chemical group 0.000 claims description 25
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 21
- 125000001931 aliphatic group Chemical group 0.000 claims description 18
- 238000005507 spraying Methods 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 239000003086 colorant Substances 0.000 claims description 14
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 12
- 238000004132 cross linking Methods 0.000 claims description 11
- 230000000295 complement effect Effects 0.000 claims description 9
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical group O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 6
- 239000004200 microcrystalline wax Substances 0.000 claims description 5
- 235000019808 microcrystalline wax Nutrition 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 3
- 238000005187 foaming Methods 0.000 claims 2
- 230000000717 retained effect Effects 0.000 abstract description 7
- 239000010985 leather Substances 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 137
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000002904 solvent Substances 0.000 description 12
- 239000000470 constituent Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 239000007921 spray Substances 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- 239000012948 isocyanate Substances 0.000 description 6
- 150000002513 isocyanates Chemical class 0.000 description 6
- 239000004922 lacquer Substances 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000003973 paint Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229920005955 Elastolit® Polymers 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920002397 thermoplastic olefin Polymers 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229920005830 Polyurethane Foam Polymers 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 239000002355 dual-layer Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000011496 polyurethane foam Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 239000012855 volatile organic compound Substances 0.000 description 3
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 2
- 239000004604 Blowing Agent Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004169 Hydrogenated Poly-1-Decene Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 210000003850 cellular structure Anatomy 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 235000019383 crystalline wax Nutrition 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- -1 diethanolamine) Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 210000003127 knee Anatomy 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- RWRDLPDLKQPQOW-UHFFFAOYSA-N tetrahydropyrrole Natural products C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 239000013008 thixotropic agent Substances 0.000 description 2
- 239000012974 tin catalyst Substances 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229920007019 PC/ABS Polymers 0.000 description 1
- 206010035148 Plague Diseases 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920006311 Urethane elastomer Polymers 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- KIQKWYUGPPFMBV-UHFFFAOYSA-N diisocyanatomethane Chemical compound O=C=NCN=C=O KIQKWYUGPPFMBV-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 229920003247 engineering thermoplastic Polymers 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 230000004313 glare Effects 0.000 description 1
- 239000000852 hydrogen donor Substances 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical class CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000019612 pigmentation Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000011495 polyisocyanurate Substances 0.000 description 1
- 229920000582 polyisocyanurate Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000002025 wood fiber Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C37/00—Component parts, details, accessories or auxiliary operations, not covered by group B29C33/00 or B29C35/00
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
- B29C44/12—Incorporating or moulding on preformed parts, e.g. inserts or reinforcements
- B29C44/14—Incorporating or moulding on preformed parts, e.g. inserts or reinforcements the preformed part being a lining
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C37/00—Component parts, details, accessories or auxiliary operations, not covered by group B29C33/00 or B29C35/00
- B29C37/0025—Applying surface layers, e.g. coatings, decorative layers, printed layers, to articles during shaping, e.g. in-mould printing
- B29C37/0028—In-mould coating, e.g. by introducing the coating material into the mould after forming the article
- B29C37/0032—In-mould coating, e.g. by introducing the coating material into the mould after forming the article the coating being applied upon the mould surface before introducing the moulding compound, e.g. applying a gelcoat
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
- B29C67/24—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 characterised by the choice of material
- B29C67/246—Moulding high reactive monomers or prepolymers, e.g. by reaction injection moulding [RIM], liquid injection moulding [LIM]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
- B60R13/00—Elements for body-finishing, identifying, or decorating; Arrangements or adaptations for advertising purposes
- B60R13/02—Internal Trim mouldings ; Internal Ledges; Wall liners for passenger compartments; Roof liners
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
- B60R13/00—Elements for body-finishing, identifying, or decorating; Arrangements or adaptations for advertising purposes
- B60R13/02—Internal Trim mouldings ; Internal Ledges; Wall liners for passenger compartments; Roof liners
- B60R13/0237—Side or rear panels
- B60R13/0243—Doors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
- B60R13/00—Elements for body-finishing, identifying, or decorating; Arrangements or adaptations for advertising purposes
- B60R13/02—Internal Trim mouldings ; Internal Ledges; Wall liners for passenger compartments; Roof liners
- B60R13/0256—Dashboard liners
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2075/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
- B60R13/00—Elements for body-finishing, identifying, or decorating; Arrangements or adaptations for advertising purposes
- B60R13/02—Internal Trim mouldings ; Internal Ledges; Wall liners for passenger compartments; Roof liners
- B60R2013/0281—Internal Trim mouldings ; Internal Ledges; Wall liners for passenger compartments; Roof liners made of a plurality of visible parts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
- B60R13/00—Elements for body-finishing, identifying, or decorating; Arrangements or adaptations for advertising purposes
- B60R13/02—Internal Trim mouldings ; Internal Ledges; Wall liners for passenger compartments; Roof liners
- B60R2013/0293—Connection or positioning of adjacent panels
Definitions
- This invention relates to automotive interior trim articles containing a panel structure mountable in an automobile vehicle to form a part of the interior thereof, and in particular to automobile interior trim articles such as instrument panels, door panels, and glove compartment doors. This invention further relates to a process for making automotive interior trim articles. Description of Related Art
- Automotive interior trim articles such as instrument panels, door panels, armrests, headrests, floor consoles, knee bolsters, and glove compartment doors conventionally have been constructed by applying a soft decorative covering over a rigid substrate mountable in an automobile vehicular body, with a cellular polyurethane padding interposed between the decorative covering and rigid substrate.
- a predetermined texture and color is usually provided to the decorative covering in an effort to simulate the appearance and feel of authentic leather.
- the preparation of a self-supporting synthetic automotive interior trim article having a dual layer decorative covering is disclosed in U.S. Patent No. 5,662,996 (corresponding to WO 93/23237), and in particular at Example 2 thereof.
- a solvent-based polyurethane lacquer is initially applied to an open mold surface as an "in-mold paint", and then is dried by evaporating off the solvent.
- a "skin" prepared from a two-part polyurethane elastomer is thereafter formed on the inner surface of the dried in-mold paint by employing specialized nozzles and application systems.
- suitable spray nozzles and systems that can be employed are disclosed in U.S. Patent Nos. 5,028,006 and 5,071,683.
- a polyurethane cellular foam layer is prepared by spraying a polyurethane reaction mixture against the polyurethane elastomer skin.
- a polyurethane or polyisocyanurate reaction mixture is applied against the opposing surface of the polyurethane cellular foam layer to obtain a rigid synthetic carrier.
- Recticel does not utilize an in-mold solvent-based lacquer in its own commercial activity. Recticel has even proscribed at least one of its customers from using its in-mold paint. Further, the use of the solvent-based lacquer as the in-mold paint plagues the preparatory method disclosed in the Recticel '996 patent with several complications and inefficiencies. For example, these lacquers contain large amounts of atmosphere-polluting volatile organic compounds (VOCs).
- VOCs atmosphere-polluting volatile organic compounds
- the panel structure comprises a layered composite structure and a reinforcing substrate, with the substrate being hidden from the vehicle interior when the panel structure is mounted in the automobile.
- the layered composite structure comprises an outer layer defining at least a portion of an at least partially-exposed exterior surface of the panel structure and an inner layer.
- At least the following steps are performed to prepare the panel structure.
- At least one water-dispersed composition comprising at least one light-stable thermoplastic polyurethane (preferably in the form of resin particles in a colloid solution dispersed in water) containing one or more pendent hydroxyl and/or carboxyl functional groups, at least one desired coloring agent, and at least one light-stable, blocked, heat-activated diisocyanate is applied onto a heated mold surface shaped to define a complementary configuration to the outer layer.
- the light-stable thermoplastic polyurethane and the blocked, heat-activated diisocyanate are heated, preferably by pre-heating the mold surface, and reacted to induce crosslinking of the thermoplastic polyurethane with the blocked, heat-activated diisocyanate. Then, the water-dispersed composition is substantially dried while on the mold surface to coalesce the resin particles into a contiguous film and thereby form the exposed outer layer.
- a rapidly reacting composition containing at least one aromatic polyisocyanate and at least one polyol is sprayed onto an inner surface of the outer layer while on the mold surface to form the inner layer comprising an aromatic polyurethane elastomer crosslinked with the polyurethane of the outer layer via residual unreacted functional groups of the blocked, heat-activated diisocyanate in the outer layer. Consequently, interfacial chemical bonding is obtained between the inner surface of the outer layer and an adjacent surface of the inner layer to form the layered composite structure.
- the layered composite structure is then united with the reinforcing substrate so that the reinforcing substrate serves to reinforce the outer layer.
- a soft cellular polyurethane foam layer can be formed intermediate the inner layer and the reinforcing substrate. Consequently, the panel structure retains the touch, color and configuration of the exposed portion and the compressing feel provided to the outer layer by the inner layer and the optional soft cellular foam intermediate layer.
- Another object of the present invention is the provision of an automotive interior trim article containing a panel structure made by the method of the present invention, and in particular the provision of a panel structure having an exterior surface which simulates the appearance and feel of authentic leather. In accordance with the principles of the present invention, this object is attained by providing an article comprising a panel structure mountable in an automobile vehicle to form a part of the interior thereof.
- the panel structure has an exterior surface at least partially exposed to the vehicle interior and an interior surface which is hidden from the vehicle interior when the panel structure is mounted to the automobile vehicle structure.
- the panel structure comprises a reinforcing substrate and layered composite structure, with a soft cellular polyurethane foam layer optionally interposed therebetween.
- the reinforcing substrate has one surface defining the interior surface of the panel structure, and an opposite surface which is united to the layered composite structure.
- the layered composite structure comprises an outer layer and an inner layer. The outer layer defines at least a portion of the exposed exterior surface of the panel structure, and has the desired touch, color, and configuration of the panel structure, as well as exhibiting good chemical resistance.
- the outer layer comprises a substantially dried, light- stable, crosslinked polyurethane formulated from a water-dispersed composition comprising at least one desired coloring agent, at least one light-stable thermoplastic polyurethane containing one or more pendent hydroxyl and/or carboxyl functional groups, and a light-stable, blocked, heat-activated diisocyanate cross-linker.
- the light-stable aliphatic thermoplastic polyurethane and the blocked, heat-activated diisocyanate are heated to thereby produce a crosslinking reaction and molded on a heated mold surface shaped to define a complementary configuration to the outer layer, and then are dried on the mold surface.
- the inner layer which is thicker than the outer layer, comprises an aromatic polyurethane elastomer formulated from a rapidly reacting composition containing at least one aromatic polyisocyanate and at least one polyol.
- the blocked, heat-activated diisocyanate serves to crosslink the aromatic polyurethane elastomer with the light-stable polyurethane of the outer layer. Consequently, the inner layer has a surface adjacent to and interfacially chemically bonded with an inner surface of the outer layer.
- the interfacial chemical bonds are formed by spraying the rapidly reacting composition onto the inner surface of the outer layer while the outer layer is retained on the mold surface.
- the reinforcing substrate serves to reinforce the outer layer while retaining the touch and color of the exposed portion and the compressing feel provided to the outer layer by the inner layer and the optionally interposed soft cellular polyurethane foam.
- the composite provided in accordance with this embodiment exhibits excellent chemical, scuff and mar resistance to external influences. These and other properties are further enhanced by the selection of an aromatic polyisocyanate, as opposed to an aliphatic polyisocyanate, for making the polyurethane inner layer.
- Physical properties exhibited by and the processability of aromatic-based elastomers exceed those of aliphatic-based elastomers in several categories that are crucial in the automobile industry. For example, the improved processability of the aromatic-based elastomers is manifested by their better sprayability, reduced run-back, faster cure rates and demolding times, excellent handling, fewer pin holes, and more uniform thicknesses.
- the aromatic-based elastomers also exhibit higher tensile and tear strengths, better elongation and "cold flex" capability, and lower cost than their aliphatic- based counterparts. These characteristics translate into faster production times and higher quality products than could be attained with aliphatic-based elastomers. Moreover, concerns over the aromatic-based elastomer becoming less stable after prolonged exposure to light are obviated, since the light-stable polyurethane outer layer masks the aromatic-based elastomer from direct exposure to sunlight.
- both the inner and outer layers of the composite are characterized by excellent extensibility, such that the composite can withstand indentation and flexure during use without causing cracking in the outer layer over a wide temperature range, such as from -30°C to 120°C.
- FIG. 1 is a perspective, partially sectioned and partially phantomed view of a completed vehicle door panel constructed in accordance with the present invention
- FIG. 2 is a perspective view of a completed vehicle instrument panel constructed in accordance with the present invention
- FIG. 3 is a sectional view of the instrument panel of FIG. 2 taken along line III-III;
- FIG. 4 is a sectional view of a mold surface showing a step of applying a water- dispersed polyurethane composition to the mold surface while heated to form a crosslinked light-stable polyurethane outer layer in accordance with the present invention
- FIG. 5 is a sectional view similar to FIG. 4 showing a step of drying the polyurethane outer layer
- FIG. 6 is a sectional view similar to FIG. 5 showing a step of obtaining an inner layer, and hence a layered composite structure, by spraying a rapidly reacting composition onto an inner surface of the outer layer while the outer layer is retained on the mold surface;
- FIG. 7 is a sectional view similar to FIG. 6 showing a step of removing the layered composite structure from the mold surface;
- FIG. 8 is a sectional view of a second mold surface showing a step of obtaining a relatively rigid polyurethane cellular foam intermediate layer by applying a reaction mixture to the layered composite structure while disposed on a second mold surface;
- FIG. 9 is a sectional view showing a step of uniting the layered composite structure on the second mold surface with a pre-formed substrate disposed on a third mold surface.
- FIG. 1 a panel structure comprising a vehicle door panel, generally designated by reference numeral 10, made by a method according to the principles of the present invention.
- the door panel 10 includes a window sill upper portion 12 and an arm rest portion 14 defining therebetween a bolster receiving portion 16.
- a lower planar rug receiving portion 18 having a rug section 20 connected thereto is disposed below the arm rest portion 14.
- the panel structure 10 has an exterior surface 10a exposed to the vehicle interior and an interior surface 10b which is hidden from the vehicle interior when the panel structure 10 is mounted in the automobile vehicle.
- the panel structure 10 includes a reinforcing (or rigid) substrate 22 having one surface defining the interior surface 10b of the panel structure 10.
- the panel structure 10 further includes a layered composite structure, generally designated by reference numeral 24, comprising an outer layer 26 defining at least a portion of the exposed exterior surface 10a of the panel structure 10 and an inner layer 28. At least a portion of the outer layer 26 is exposed to the vehicle interior, while a portion of the outer layer may be hidden from view by a decorative or other masking item. For example, in FIG. 1, the lower planar rug receiving portion 18 of the outer layer 26 is covered by the rug section 20 and, therefore, is not exposed to the vehicle interior.
- the inner layer 28, which is relatively thick in comparison to the outer layer 26, has an outer surface 28a (FIG. 6) adjacent to and interfacially chemically bonded with an inner surface 26b (FIGS. 5 and 6) of the outer layer 26.
- an intermediate layer 30 containing a relatively rigid (or semi-rigid) polyurethane cellular foam filler is interposed between the inner layer 28 and the rigid substrate 22.
- the reinforced substrate 22 should have sufficient strength to reinforce and mount the outer layer 26, inner layer 28, and intermediate layer 30, and should have sufficient rigidity to permit the composite to be mounted into a vehicular sub-structure.
- the method of the present invention utilizes a first mold component or part 32 having a first mold surface 34.
- the first mold component 32 preferably is formulated by electrolytically depositing nickel over a rigid cast epoxy substrate which is secondarily removed at the end of the deposition/plating process to yield a self-supporting mold capable of being mounted and controlled in a tooling module.
- the first mold surface 34 is shaped to define a configuration that substantially complements to the desired configuration of the outer layer 26, and is grained to define a texture that substantially complements the desired texture of the outer layer 26 and simulates real leather.
- FIG. 4 illustrates the first step in the present invention and, in accordance with this step, the outer layer 26 is obtained by applying, preferably by spraying, a water-dispersed composition 36 onto the first mold surface 34.
- the water-dispersed composition comprises at least one light-stable aliphatic thermoplastic polyurethane containing one or more pendent hydroxyl and/or carboxyl functional groups, at least one desired coloring agent, and at least one blocked, heat-activated (preferably aliphatic) diisocyanate.
- the first mold surface 34 should be heated to a sufficient temperature to drive the crosslinking reaction, but should not be so high as to cause delamination of the composition 36 from the mold surface 34.
- the first mold surface 34 is heated to a temperature in a range of from about 60°C (140°F) to about 71.1 °C (160°F).
- the heating of the first mold surface 34 to such elevated temperatures prior to application of the water-dispersed composition 36 thereto also serves to melt and disperse semi-permanent mold releasing agents, such as microcrystalline wax mold releasing agents, applied to the first mold surface 34.
- the heated mold surface thereby serves to evaporate the wax dispersants and leave a thin residue that does not collect in the intricate grain detail of the first mold surface 34.
- the light-stable aliphatic thermoplastic polyurethane and the blocked, heat-activated aliphatic diisocyanate constituents can be stably premixed, and stored for prolonged periods of time at room temperature before application.
- the water-dispersed composition 36 may be formed from a colloid solution of resin particles, which is added to water to disperse the resin particles in the water.
- the crosslinked light-stable polyurethane is substantially dried while being retained on the first mold surface 34 to obtain the outer layer 26.
- the crosslinked light-stable polyurethane can be subjected to a heat source 40 to induce evaporation of the water and at least some of the solvent therefrom and coalesce the resin particles to thereby form the outer layer 26 with an outer surface 26a adjacent to the first mold surface 34.
- a heat source 40 is preferably integrated with the first mold 32, and preferably heats the first mold surface 34 to an elevated temperature of about 65.9°C (150°F) or higher. At least a portion of the outer surface 26a of the outer layer 26 has the desired touch, color, and grain-like configuration of the panel structure 10.
- the outer layer 26 has a thickness in a range of from about 0.0025 cm to about 0.0038 cm (that is, from about 1.0 mils to about 1.5 mils; or from about 0.001 inch to about 0.0015 inch).
- the particular coloring agent selected can directly influence the desired thickness of the outer layer 26.
- Darker colors, such as grays and browns usually only require a relatively small film thickness to mask the color of the hidden inner layer 28, whereas lighter colors such as reds and blues usually dictate the provision of a relatively larger thickness to obtain an opaque, non- transparent outer layer 26 that conceals the inner layer 28 from view and protects the inner layer from sunlight degradation.
- the polyurethane elastomer inner layer 28 is formed by spraying a rapidly reacting composition 42 onto the inner surface 26b of the outer layer 26 while the outer layer 26 is retained on the first mold surface 34 in a substantially dry state.
- the rapidly reacting composition 42 contains at least one aromatic polyisocyanate and at least one polyol, which react with each other to form the non-light-stable polyurethane elastomeric inner layer 28.
- the term elastomer encompasses any resilient polymer composition stretchable under moderate tension and compressible and having a relatively high tensile strength and memory so that, upon release of the tension, the elastomer retracts into and recovers its original dimensions or dimensions substantially similar to its original dimensions.
- the polyol constituent of the rapidly reacting composition 42 can contain one or more pendent hydroxyl and/or carboxyl functional groups that are highly reactive with unreacted functional groups of blocked, heat-activated aliphatic diisocyanate in the outer layer 26 that have not reacted with the pendent functional groups of the polyurethane of the outer layer 26. Unreacted functional groups of the blocked, heat-activated aliphatic diisocyanate penetrate into the inner layer 28 and react with the pendent functional groups of the polyol constituent.
- the blocked, heat-activated aliphatic diisocyanate crosslinks the polyurethane of the outer layer 26 with the polyurethane elastomer of the inner layer 28 and thereby forms an interfacial chemical bond between the inner surface 26b of the outer layer 26 and the adjacent outer surface 28a of the inner layer 28.
- the layered composite structure 24 is thus obtained. If the crosslinking is performed under optimum crosslinking conditions, the boundary between the outer and inner layers 26 and 28 of the layered composite structure 24 can become visually indistinct, such that a transition phase appears at the interface of the two layers.
- interfacial chemical bonding encompasses, but is not limited to, such crosslinking reactions in which the interfacing boundary between the outer and inner layers 26 and 28 is visually indistinct and inseparable.
- provisions should be taken to ensure that an adequate interfacial chemical bond is achieved between the inner surface 26b of the outer layer 26 and the adjacent outer surface 28a of the inner layer 28.
- the rapidly reacting composition 42 generally should be sprayed within six minutes, and preferably within two to four minutes, of completing the application of the water-dispersed composition 36 to the first mold surface 34.
- condensation reactions release water, which in excess amounts can act as a blowing agent and undesirably increase the cellularity of the inner layer 28 and interfere with the interfacial chemical bond.
- the interfacial chemical bond is further enhanced by separately storing the highly reactive polyol and aromatic polyisocyanate constituent components of the rapidly reacting composition 42 in separate storage chambers and spraying these components on the inner surface 26b of the outer layer 26 so as to avoid contact between these components until spraying is conducted.
- a suitable dual nozzle spraying mechanism for accomplishing this task is disclosed in U.S. Patent Nos. 5,028,006 and 5,071,683.
- the outer layer 26 and the surrounding atmosphere e.g., humidity levels
- the concentration of such moisture should not be so great as to permit the water to substantially interfere with the reaction between the polyol and polyisocyanate constituents of the rapidly reacting composition 42.
- Undesirable reactions between the water and the polyisocyanate can disrupt the stoichiometric balance between the polyol and the polyisocyanate, leaving localized unreacted polyol deposits behind on the layered composite structure 24.
- the water also can serve as a blowing agent, reacting with the polyisocyanate to release carbon dioxide which imparts a cellular structure to the inner layer 28. Excess amounts of water also can deleteriously interfere with the crosslinking reaction effected via the polyol and the residual reactive sites of the blocked, heat-activated aliphatic diisocyanate.
- the rapidly reacting composition 42 is preferably applied to the inner surface 26a of the outer layer 26 at an elevated temperature to advance these objectives.
- Suitable temperatures to which the first mold component 32 can be heated range, by way of example and without limitation, from about 60°C (140°F) to about 71.1 °C (160°F).
- the inner layer 28 can have a thickness in a range of from about 0.10 cm to about 0.15 cm (that is, from about 40 mils to about 60 mils; or from about 0.040 inch to about 0.060 inch).
- FIG. 7 illustrates the next step of the present invention.
- the layered composite structure 24 is demolded (i.e., removed) from the first mold surface 34.
- demolding can take place at a mold temperature of, for example, about 60°C (about 140°F).
- Demolding the aromatic-based elastomer is a much less labor intensive, tedious, and time consuming task than demolding the aliphatic-based elastomer. Formation of tears in or undue stretching of the layered composite structure 24 during demolding, which can irreversibly ruin and thereby necessitate disposal of the layered composite structure 24 as scrap, is much less likely to occur with the aromatic-based elastomer.
- the mold surface 34 can be pretreated with a releasing agent.
- exemplary releasing agents include, without limitation, high molecular weight microcrystalline wax mold releases, such as Chem-Trend PRC 7140, supplied by Chem-Trend, Inc. of Howell, Michigan, or PRC 2006, also supplied by Chem-Trend. These mold releasing agents dry quickly on a heated mold within about 5 to about 10 seconds and form a release barrier between the grained mold surface 34 and the outer layer 26.
- the layered composite structure 24, including the combination of the outer and inner layers 26 and 28, can be examined for defects with a light source (not shown) while the layered composite structure 24 is positioned on a transparent substrate (not shown).
- defects usually are present as cosmetic blemishes in the outer layer 26, and may include the presence of tears and rupturable portions lacking sufficient thicknesses to withstand stresses associated with demolding or the further processing steps, especially the uniting step. If minor and isolated, such localized defects can be remedied by post application of additional water-dispersed composition 36 onto the backside 28b of the inner layer 28.
- the layered composite structure 24 optionally can be maintained against the first mold surface 34 until completion of the panel structure 10.
- the layered composite structure 24 is placed on a second mold surface 52 of a second mold part 50.
- the second mold surface 52 also is shaped to define a complementary configuration to the outer layer 26.
- a reactive mixture 44 for forming a semi-rigid cellular foam such as a polyurethane semi-rigid cellular foam, is applied to an inner surface 28b of the inner layer 28 while the composite structure 24 is disposed on the second mold surface 52 to form the intermediate layer 30.
- the reactive mixture 44 can be applied, for instance, by employing high pressure impingement mixing and a mix-head nozzle.
- the second mold component 50 is generally heated to a temperature in a range of from about 35 °C to about 45 °C, and more preferably in a range of from about 35 °C to about 40 °C, during application of the reactive mixture.
- the mixture 44 which is typically relatively viscous, is in a transient state of reaction during application to the second mold component 50 and begins to foam within seconds of application.
- the intermediate layer can have a thickness in a range of from about 5 mm to about 12 mm.
- a third cooperating mold part or component 60 carrying the pre-formed rigid substrate 22 is moved into cooperating relation with the second mold component 50, as shown in FIG. 9.
- the third mold component 60 has a third mold surface 62 (FIG. 8) which is shaped to define the interior surface 10b of the panel structure 10.
- the reactive mixture 44 is foamed and cured, preferably under heat of approximately 43.3 °C (110°F) and a self-generated cavity pressure of about 0.8 atm to form the intermediate layer 30.
- the semi-rigid polyurethane cellular foam serves to unite the layered composite structure 24 with the pre-formed substrate 22 disposed on a third mold surface 62.
- the panel structure including the combination of the layered composite structure 24, the substrate 22, and the intermediate layer 30 then can be removed from the mold parts 50 and 60 and additional components, such as the rug section 20, can be affixed.
- the layered composite structure 24 and/or the intermediate layer 30 can be eliminated from the hidden lower planar rug receiving portion 18 (or other portions that are hidden from the vehicle interior when the panel structure is mounted in the automobile vehicle) of the resultant panel structure 10 depicted in FIG. 1.
- the lower planar rug receiving portion 18 is thereby characterized by having the rigid substrate 22 and optionally the intermediate layer 30 directly adjacent to the rug section 20.
- a non-foamable adhesive can be selected for uniting the layered composite structure 24 to the reinforcing substrate 22.
- multiple water-dispersed compositions containing different coloring agents can be respectively applied to different portions of the panel structure to produce discretely masked colors. Where the selected color or colors are to be changed, in practice it has been found that minimal downtime (on the order of about 0.5 hours) is common.
- the outer layer 26 can exhibit a dualtone or multitone appearance.
- This variant embodiment can be accomplished, for example, by abrasive treatment of a portion of the mold surface of the tooling. The greater the amount of abrasive treatment, the duller the appearance of the outer layer 26.
- a dualtone appearance can be especially desirable for instrument panels, since the upper region of an instrument panel generally should have a low gloss in order to reduce reflectance and veiling glare.
- the layered composite structure 24 can be retained in the first mold component 32 instead of being demolded and transferred to a second mold component 50 for the uniting step.
- the layered composite structure 24 can be returned to the first mold component 32 after being examined and treated.
- a secondary or alternative heat source can be applied for activating the reaction between the light-stable aliphatic thermoplastic polyurethane and the blocked, heat-activated aliphatic diisocyanate.
- the water-dispersed composition 36 can be preheated before being applied to the first mold surface 34, such that the first mold surface 34 does not have to be heated to initiate the reaction between the heat-activated aliphatic diisocyanate and the light-stable aliphatic thermoplastic polyurethane.
- the reactive mixture 44 for forming the polyurethane semi-rigid cellular foam 30 can be applied to the surface of the substrate 22 instead of the layered composite structure 24.
- the second and third mold components 50 and 60 can be cooperatively engaged to define a cavity between the inner surface 28b of the inner layer 28 and the outer surface of the substrate 22, with the reactive mixture 44 thereafter being injected between the rigid substrate 22 and the composite 24.
- the water-dispersed composition 36 used to prepare the outer layer 26 comprises at least one light-stable aliphatic thermoplastic polyurethane. at least one desired coloring agent, and at least one blocked, heat-activated aliphatic diisocyanate.
- the light-stable aliphatic thermoplastic polyurethane is preferably prepared from a high molecular weight aliphatic thermoplastic polyurethane containing hydroxyl and/or carboxyl pendent functional groups which are chemically reactive with the blocked, heat-activated aliphatic diisocyanate.
- the average molecular weight of the thermoplastic polyurethane preferably is in a range of from about 5000 to about 7000, and more preferably about 6000.
- thermoplastic polyurethane and blocked, heat-activated aliphatic diisocyanate can be obtained from Titan Finishes Corp. of Detroit, Michigan under the trade designation PROTOTHANE WR, WATER BASED IN-MOLD COATING.
- the aliphatic diisocyanate may be cyclic or non-cyclic, but should be light stable.
- diisocyanates also encompasses prepolymers having two -NCO groups which are reactive with the thermoplastic polyurethane.
- An exemplary aliphatic diisocyanate is hexamethylene diisocyanate (HMI), which is available from Bayer, Rhone Poulenc, and Nippon Polyurethane.
- HMI hexamethylene diisocyanate
- the weight ratio of thermoplastic polyurethane to blocked, heat-activated aliphatic diisocyanate is about 8 to 1 by volume, although this ratio can vary some due to the selection of the thermoplastic polyurethane and diisocyanate.
- the water-dispersed composition 36 can be prepared by providing thermoplastic polyurethane component as a colloidal solution in a solvent such as N-methyl pyrrolidone, then dispersing the solution by adding water, the coloring agent, and conventional additives, if desired. Sufficient water (about 61.1 % by weight) can be added so that the solvent concentration in the water-dispersed composition 36 is about 8.1% by weight before drying.
- the optional additives in the water-dispersed composition 36 can include, without limitation, any combination of the following: heat and ultra-violet light stabilizers, pH stabilizers to maintain an alkaline state of dispersion, plasticizers, antioxidants, dulling agents, surfactants, colloidal protectants to maintain particles in suspension, carbon black, thixotropic agents (e.g., hydroxy methyl cellulose), and fillers such as clay particles.
- the water-dispersed composition 36 can contain, for example, about 25% to about 35% solids by weight, and more preferably about 29% solids by weight, about 10% to about 80% water by weight, and more preferably about 61% water by weight, and about 6% to 10% solvents by weight, depending on desired color and additives.
- An insufficient amount of water in the composition 36 can adversely affect the viscosity of the composition 36 and thus adversely affect the application of the water-dispersed composition 36 onto the mold surface 34.
- an excess amount of water in the composition 36 can significantly alter the sprayability and coating efficiency of the water-dispersed composition 36 to prolong the time needed to dry the outer layer 26.
- thermoplastic polyurethane solution a solution of the blocked, heat- activated aliphatic diisocyanate, which can include as a solvent, for example, l-methyl-2- pyrrolidine and/or 4-hydroxy-4-methyl-2-pentanone.
- a discussion of blocked isocyanates is included in Practical Chemistry of Polyurethanes and Diisocyanates, Akron Polymer Laboratories, David Russell (1991), the complete disclosure of which is incorporated herein by reference.
- the blocked, heat-activated aliphatic diisocyanate is preferably maintained at room temperature and protected from heat until use.
- the blocked, heat-activated aliphatic diisocyanate reacts with the hydroxyl and/or carboxyl groups of the thermoplastic polyurethane to crosslink the thermoplastic polyurethane with itself or with polyol constituents of the rapidly reacting composition 42.
- Exemplary polyisocyanates that can be selected for the rapidly reacting composition 42 employed to prepare the inner layer 28 include diisocyanates having aromatic closed-ring structures, such as diphenylmethane diisocyanate prepolymer (MDI prepolymer), which can be obtained from BASF Corp. of Wyandotte, ML under the trade designation ELASTOLIT M50555T, ISOCYANATE, NPU U05275, or diphenylmethane-4,4'-diisocyanate (MDI), or mixed isomers of MDI or mixtures of the above, which are available from BASF or Dow Chemical Corp. of Midland, MI, Mobay (Bayer) Chemical Corp. of Baytown, Texas, or ICI America of Geismar, LA.
- MDI prepolymer diphenylmethane diisocyanate prepolymer
- MDI diphenylmethane diisocyanate prepolymer
- MDI diphenylmethane diisocyanate prepolymer
- MDI
- non-light-stable aromatic polyisocyanates are very desirable for use in the inner layer in view of the higher rate of reactivity and completion of property development and better physical properties (e.g., tensile strength, elongation, and tear strength) of these non-light-stable aromatic polyisocyanate when compared to light-stable aliphatic-based isocyanates such as isophorone diisocyanates, in which the -NCO groups are sterically hindered due to their spatial arrangement at either end of the molecule.
- the aromatic diisocyanates used in this invention preferably have -NCO groups directly attached to the aromatic ring.
- the aromatic diisocyanates yield faster rates of reaction because of the arrangement and reactivity of the -NCO groups on the aromatic ring structure (e.g., in diphenylmethane diisocyanate) and the availability of the -NCO groups for reaction with the hydrogen donors of the -OH type residing on the organic chain of the polyols of the rapidly reacting composition 42.
- Suitable polyols for this rapidly reacting composition 42 include, without limitation, polyether polyols having average molecular weights in a range of from about 200 to about 2000 and containing one or more pendent hydroxyl and/or carboxyl groups in addition to primary hydroxyl groups, which can chemically react with unreacted functional -NCO groups of the blocked, heat-activated aliphatic diisocyanate and the hydroxyl and/or carboxyl pendent functional groups of the polyurethane of the outer layer 26.
- An exemplary polyol is ELASTOLIT M50555R NPU U05274 from BASF Corp. of Wyandotte, MI.
- the rapidly reacting composition 42 can also contain appropriate additives, including, by way of example and without limitation, any combination of the following: heat and ultra- violet light stabilizers, pH stabilizers, antioxidants, dulling agents, surfactants, carbon black, chain extenders (e.g., ethylene glycol), thixotropic agents (e.g., amorphous silica), fillers such as clay particles, and catalysts such as tin catalysts (e.g., dibutyltin dilaurate).
- appropriate additives including, by way of example and without limitation, any combination of the following: heat and ultra- violet light stabilizers, pH stabilizers, antioxidants, dulling agents, surfactants, carbon black, chain extenders (e.g., ethylene glycol), thixotropic agents (e.g., amorphous silica), fillers such as clay particles, and catalysts such as tin catalysts (e.g., dibutyltin dilaurate).
- the semi-rigid polyurethane cellular foam of the intermediate layer 30 can be employed to form the semi-rigid polyurethane cellular foam of the intermediate layer 30.
- the polyisocyanate blend can include methylene diisocyanate.
- the semi-rigid polyurethane cellular foam also can contain appropriate additives, including, by way of example and without limitation, any combination of the following: surfactants, antioxidants, fillers, stabilizers, catalysts such as tin catalysts (e.g., dibutyl tin dilaurate) and amines (e.g., diethanolamine), and small amounts of foaming agents such as water.
- the rigid substrate 22 can be selected from any material possessing the requisite strength to reinforce and mount the outer layer 26, inner layer 28, and intermediate layer 30. Suitable materials include polyolefins, such as polypropylene and ethylene-propylene copolymers, thermoplastic olefins (TPOs), and thermoplastic polyolefin elastomers (TPEs).
- TPOs thermoplastic olefins
- TPEs thermoplastic polyolefin elastomers
- engineering thermoplastics may be selected. These include injection molding thermoplastics, such as acrylonitrile butadiene styrene (ABS), polycarbonate (PC), a PC/ABS alloy, thermoplastic polyurethane (TPU), styrene maleic anhydride (SMA), and reaction injection molded polyurethanes (RRJM). Other materials, such as metals, metal alloys, wood-fiber composites, or any combination thereof, can also be used.
- the reinforcing substrate 22 can optionally also include reinforcement nanoparticles comprising platelet minerals dispersed in the desired polymer in desired ratios.
- the components can be blended by general techniques known to those skilled in the art. For example, the components can be blended and then melted in mixers or extruders.
- FIGS. 2 and 3 An instrument panel prepared in accordance with the method of the present invention is illustrated in perspective and cross- sectional views in FIGS. 2 and 3, respectively, and is generally designated by reference numeral 100.
- the instrument panel 100 is shown in cross-section in FIG. 3, and includes a substrate 122, an outer layer 126 and an inner layer 128 (collectively a layered composite structure, generally designated by reference numeral 124), and an intermediate layer 130.
- a microlayer coating of a crystalline wax mold release agent (Chem-Trend PRC 7140 with naphtha (petroleum naphtha) solvent under stirring) containing 2% solids was sprayed onto a grained surface of a nickel electroform tooling while the tooling was maintained (throughout the process) at a constant temperature of 60°C.
- the crystalline wax was allowed to dry over a 15 second period, then was sprayed with catalyzed, color-keyed water-based composition comprising Titan Finishes Corp.'s PROTOTHANE WR, WATER BASED IN-MOLD
- COATING (containing 61.1 wt% water and 8.1 wt% solvent), hexamethylene diisocyanate from Bayer, and medium dark neutral (or light brown pigmentation) to yield an outer layer having a thickness of about 0.025 mm.
- the water was then evaporated to leave a contiguous film of coalesced resin particles with some residual solvent.
- the mold with the outer layer disposed thereon was moved to another station (taking approximately 30 seconds), where a two-part urethane elastomer was sprayed onto the surface of the inner layer.
- ELASTOLIT M50555T, ISOCYANATE, NPU U05275 isocyanate with a free -NCO weight percent of 22.6 to 23.2 and ELASTOLIT M50555RNPU U05274 polyol from BASF with an equivalent weight of 350 g/mol and a hydroxyl number of 160 were delivered separately through heated lines at 60°C using high pressure metering pumps at 1250 psi delivery pressure.
- the weight ratio of polyol to isocyanate was 1.9: 1.
- a feedback loop controller was used to bring the two components together in a high pressure impingement mixer within a valve controller and thereby combined the two reactive components by passing them through a sequential static mixer and spray orifice that delivers a controlled shape stream of mixed liquid at 20.0 g/sec.
- a robotic arm served to dispose the discharge from the spray orifice in a controlled and pre-programmed manner (as is known in the art) to coat the outer layer with an inner layer having a thickness of 1.0 ⁇ 0.1 mm of thickness.
- the valve controller and spray orifice are flushed with a non-flammable solvent.
- the polyurethane elastomer chemically bonds with the residual reactive sites of the outer layer to form a layered composite structure with interfacial chemical bonding.
- the layered composite structure is then demolded and inspected.
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Laminated Bodies (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
- Polyurethanes Or Polyureas (AREA)
- Vehicle Interior And Exterior Ornaments, Soundproofing, And Insulation (AREA)
- Moulding By Coating Moulds (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US8659398P | 1998-05-22 | 1998-05-22 | |
US86593P | 1998-05-22 | ||
PCT/CA1999/000424 WO1999061216A1 (en) | 1998-05-22 | 1999-05-21 | Decorative automotive interior trim articles with integral in-mold coated polyurethane aromatic elastomer covering and process for making the same |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1079962A1 true EP1079962A1 (de) | 2001-03-07 |
EP1079962B1 EP1079962B1 (de) | 2004-01-21 |
Family
ID=22199602
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99920485A Expired - Lifetime EP1079962B1 (de) | 1998-05-22 | 1999-05-21 | Dekorinnenteile für autos mit in der form beschichteter, integrierter elastomerabdeckung aus aromatischem polyurethan und verfahren zur herstellung derselben |
Country Status (11)
Country | Link |
---|---|
US (1) | US6544449B1 (de) |
EP (1) | EP1079962B1 (de) |
JP (1) | JP2002516194A (de) |
KR (1) | KR20010043259A (de) |
CN (1) | CN1120080C (de) |
AT (1) | ATE258108T1 (de) |
AU (1) | AU763172B2 (de) |
BR (1) | BR9910600A (de) |
CA (1) | CA2321707A1 (de) |
DE (1) | DE69914322T2 (de) |
WO (1) | WO1999061216A1 (de) |
Families Citing this family (86)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU744634B2 (en) * | 1997-04-18 | 2002-02-28 | Magna Seating Inc. | Decorative automotive interior trim articles with cast integral light stable covering and process for making the same |
EP0995568A1 (de) * | 1998-10-21 | 2000-04-26 | Recticel | Verfahren zum Herstellen eines geformten mehrschichtigen Kunststoffteiles und danach erhaltenes Teil |
EP1174458A1 (de) * | 2000-07-20 | 2002-01-23 | Huntsman International Llc | Expandierte thermoplastische Polyurethane |
DE10059762A1 (de) * | 2000-11-30 | 2002-06-06 | Magna Eybl Systemtechnik Gmbh | Verbundteil und Verfahren zu dessen Herstellung |
EP1387750A1 (de) * | 2001-05-08 | 2004-02-11 | G.I. Plastek Limited Partnership | Anordnung und verfahren zur herstellung eines in der form klarschichtigen verbundwerkstoffs |
US6890586B2 (en) | 2001-08-21 | 2005-05-10 | G.I. Plastek Limited Partnership | System and method of making an in-mold clear-coated composite |
US6682818B2 (en) | 2001-08-24 | 2004-01-27 | L&L Products, Inc. | Paintable material |
CA2413493C (en) * | 2001-12-03 | 2013-02-05 | Red Spot Paint & Varnish Co., Inc. | In-mold-coated automotive interior and other products, and methods for manufacturing same |
US6811864B2 (en) | 2002-08-13 | 2004-11-02 | L&L Products, Inc. | Tacky base material with powder thereon |
US20040056382A1 (en) * | 2002-09-19 | 2004-03-25 | Shaner Kenneth W. | Method of molding a vehicle trim component |
ATE525188T1 (de) * | 2003-10-16 | 2011-10-15 | Johnson Controls Tech Co | Fahrzeugteil und herstellungsverfahren für ein fahrzeugteil |
US20050127575A1 (en) * | 2003-12-15 | 2005-06-16 | Dry Alan G. | Method of forming a vehicle trim panel |
EP1577166B1 (de) | 2004-02-18 | 2010-12-01 | Grammer Ag | Verfahren zur Herstellung einer hautartigen Verkleidung, insbesondere für Kraftfahrzeug-Ausstattungsteile. |
US20050186388A1 (en) * | 2004-02-24 | 2005-08-25 | Mekas David E. | Automotive interior trim assembly with soft feel |
US20050183897A1 (en) * | 2004-02-24 | 2005-08-25 | Lear Corporation | Two-shot co-injected automotive interior trim assembly and method |
US7070221B2 (en) * | 2004-03-08 | 2006-07-04 | Lear Corporation | Automotive interior trim component with soft feel |
US7077456B2 (en) * | 2004-03-11 | 2006-07-18 | Lear Corporation | Automotive interior trim assembly and pad insertion |
US7871119B2 (en) * | 2004-04-30 | 2011-01-18 | International Automotive Components Group North America, Inc. | Door trim panel with dual density bolster armrest and integrated components |
US7367103B2 (en) * | 2004-06-11 | 2008-05-06 | International Automotive Components Group North America, Inc. | Method of forming a vehicle component |
US7104590B2 (en) * | 2004-07-01 | 2006-09-12 | Lear Corporation | Vehicle trim panel with integral nibbed armrest |
US20060006568A1 (en) * | 2004-07-06 | 2006-01-12 | Lear Corporation | Method of making a grab handle |
US7344666B2 (en) * | 2004-07-06 | 2008-03-18 | International Automotive Components Group North America, Inc. | Interior vehicle trim panel having a sprayed expanded polyurethane layer and method and system of making same |
US7147808B2 (en) * | 2004-07-06 | 2006-12-12 | Lear Corporation | Vehicle part with integrated impact management feature and method of making same |
US7033660B2 (en) * | 2004-07-07 | 2006-04-25 | Lear Corporation | Method of making an interior trim panel for a door and an article made thereby |
US7032954B2 (en) * | 2004-07-15 | 2006-04-25 | Lear Corporation | Automotive ashtray and method for making the same |
US7086683B2 (en) * | 2004-07-15 | 2006-08-08 | Lear Corporation | Sunvisor attachment for vehicles and method for making the same |
US20060012205A1 (en) * | 2004-07-15 | 2006-01-19 | Bogdan Radu | Automotive storage compartment and method for making the same |
FR2873333B1 (fr) * | 2004-07-20 | 2006-11-17 | Cera | Siege de vehicule automobile comprenant un dispositif de mise en rotation de la partie superieure |
US20060024507A1 (en) * | 2004-07-29 | 2006-02-02 | Lear Corporation | Method for preparing a spray urethane skin having a clear coat for vehicle interior trim components and skins made thereby |
US7273572B2 (en) * | 2004-08-04 | 2007-09-25 | International Automotive Components Group North America, Inc. | Method of making an interior panel for a door and an article made thereby |
US7195725B2 (en) * | 2004-08-04 | 2007-03-27 | Lear Corporation | Method of making an integrated door inner panel and an article made thereby |
US7059461B2 (en) * | 2004-08-05 | 2006-06-13 | General Motors Corporation | Torque-transmitting apparatus |
US20060030630A1 (en) * | 2004-08-05 | 2006-02-09 | Lear Corporation | System, method and composition for forming composite sprayed polyurethane skins having an expanded polyurethane layer |
US20060061127A1 (en) * | 2004-09-20 | 2006-03-23 | Emerling David M | Molded automotive visor |
US20060068193A1 (en) * | 2004-09-29 | 2006-03-30 | Lear Corporation | Method and apparatus for making a trim panel with a self-skinning blown elastomer component |
US20060066088A1 (en) * | 2004-09-30 | 2006-03-30 | Hier Michael J | Inflatable airbag cushion formed with a blown elastomer core and methods of using and manufacturing same |
US20060073322A1 (en) * | 2004-10-01 | 2006-04-06 | Lear Corporation | Low density spray polyurethane for automobile interior applications |
US7156437B2 (en) | 2004-10-19 | 2007-01-02 | Lear Corporation | Automotive trim part with applique and method of making same |
US20060082109A1 (en) * | 2004-10-20 | 2006-04-20 | Hier Michael J | Method of making an automotive trim assembly having an integrated airbag door |
US7458604B2 (en) * | 2004-10-20 | 2008-12-02 | International Automotive Components Group North America, Inc. | Automotive trim assembly having an integrated airbag door |
US20060091574A1 (en) * | 2004-11-03 | 2006-05-04 | Lear Corporation | Interior vehicle trim panel having a sprayed expanded polyurethane layer and method and system of making same |
US20060091575A1 (en) * | 2004-11-03 | 2006-05-04 | Lear Corporation | Method and system for making interior vehicle trim panel having sprayed skin |
US7108312B2 (en) * | 2004-11-09 | 2006-09-19 | Lear Corporation | Vehicle door trim bolster with multi-feel cover and method of making the same |
US20060099395A1 (en) * | 2004-11-09 | 2006-05-11 | Cowelchuk Glenn A | Automotive interior trim assembly and method |
US7192074B2 (en) * | 2004-11-10 | 2007-03-20 | Lear Corporation | Automotive compartment having an integrated spring mechanism and method of making the same |
US7332207B2 (en) * | 2004-12-15 | 2008-02-19 | Visteon Global Technologies, Inc. | Component for a vehicle interior and a method of assembly |
DE102004062510A1 (de) | 2004-12-24 | 2006-07-06 | Bayer Materialscience Ag | Verfahren zum Formen und Beschichten eines Substrats |
US20060216479A1 (en) * | 2005-03-22 | 2006-09-28 | Lear Corporation | Two-shot, co-injected trim panel |
US20060222775A1 (en) * | 2005-03-24 | 2006-10-05 | Lear Corporation | System, method and composition for forming composite sprayed polyurethane skins having a low density expanded polyurethane layer |
DE102005023945A1 (de) * | 2005-05-20 | 2006-12-07 | Polytec Interior Gmbh | Mehrfarbige Innenausstattungskomponenten |
DE102005024495A1 (de) * | 2005-05-27 | 2006-11-30 | Isl-Chemie Gmbh & Co. Kg | Wässrige 2-Komponenten-Lackformulierung und deren Verwendung bei der Herstellung von Formteilen |
US7284784B2 (en) * | 2005-06-08 | 2007-10-23 | Lear Corporation | Automotive bolster with soft feel and method of making the same |
DE102005028355A1 (de) * | 2005-06-18 | 2006-12-21 | Volkswagen Ag | Innenverkleidungsteil für Kraftfahrzeuge sowie Verfahren zur Herstellung eines Innenverkleidungsteils |
DE102005044823B3 (de) * | 2005-09-20 | 2007-05-16 | Airbus Gmbh | Verfahren und Vorrichtung zum Aufbringen dünner Materiallagen auf eine Reliefform |
US7300268B2 (en) * | 2005-12-15 | 2007-11-27 | Lear Corporation | Low-density part injection molding system |
US20070145641A1 (en) * | 2005-12-22 | 2007-06-28 | Lear Corporation | Interior vehicle trim panel having colored dual density composite spray elastomer skin and system and method for making the same |
EP1820686B1 (de) * | 2006-02-20 | 2016-04-13 | Volvo Car Corporation | Panel |
CA2648485C (en) * | 2006-04-07 | 2015-03-03 | Basf Aktiengesellschaft | A method of forming a composite article in a mold |
US7829003B2 (en) * | 2006-04-20 | 2010-11-09 | Basf Corporation | Method of making an article |
DE102006019007B3 (de) * | 2006-04-25 | 2007-06-28 | Krauss-Maffei Kunststofftechnik Gmbh | Verfahren zur Herstellung eines beschichteten Verbundbauteils |
BRPI0621754B1 (pt) | 2006-05-30 | 2017-05-16 | Recticel Automobilsysteme Gmbh | método para a produção de uma película de poliuretano compósita elastomérica flexível, e, película de poliuretano compósita elastomérica flexível |
DE102006031442A1 (de) * | 2006-07-05 | 2008-01-10 | Isl-Chemie Gmbh & Co. Kg | In-Mold-Coating Verfahren zur Herstellung von Formteilen unter Verwendung wässriger 2-Komponenten-Lackformulierung |
DE102006052316A1 (de) * | 2006-11-07 | 2008-05-08 | Kraussmaffei Technologies Gmbh | Verfahren und Vorrichtung zur Herstellung eines aus mehreren Komponenten bestehenden Kunststoff-Bauteils |
WO2010066294A1 (de) * | 2008-12-10 | 2010-06-17 | Sulzer Metco Ag | Verfahren zur herstellung eines körpers mit einer thermisch gespritzten oberflächenschicht, körper mit einer thermisch gespritzten oberflächenschicht, sowie verwendung des verfahrens zur herstellung eines körpers |
CN102596862B (zh) | 2009-05-15 | 2015-09-30 | 康明斯过滤Ip公司 | 表面聚结器 |
US20120164381A1 (en) * | 2010-10-11 | 2012-06-28 | Paul Morgan | In-mold coated articles having controlled surface morphology and associated methods for manufacturing same |
AU2011202857B2 (en) * | 2011-06-15 | 2015-09-17 | Nicola Schoots | Improved polyurethane panel |
US8668988B2 (en) * | 2011-06-15 | 2014-03-11 | Nicola Schoots | Polyurethane panel |
CN102409553B (zh) * | 2011-09-16 | 2013-06-19 | 东台市富安合成材料有限公司 | 一种基于原位聚合法制备不含溶剂的汽车内饰革方法 |
DE102012211951A1 (de) * | 2012-07-09 | 2014-01-09 | Wiegand Gmbh | Zierteil für Kraftfahrzeuge und Verfahren zu seiner Herstellung |
US10058808B2 (en) | 2012-10-22 | 2018-08-28 | Cummins Filtration Ip, Inc. | Composite filter media utilizing bicomponent fibers |
EP2818488B1 (de) | 2013-06-24 | 2021-10-13 | 3M Innovative Properties Company | Lackersatzfolie mit Polymerschicht, enthaltend Polyurethan |
CN105408082A (zh) * | 2013-07-31 | 2016-03-16 | 株式会社普利司通 | 发泡成型构件的制造方法和冲击吸收构件 |
US20150367541A1 (en) * | 2014-06-19 | 2015-12-24 | GM Global Technology Operations LLC | Vehicle interior trim components and associated methods |
CN105891924B (zh) * | 2015-02-13 | 2019-07-09 | 3M创新有限公司 | 具有高温稳定性的柔性微球制品 |
CN107429106B (zh) | 2015-03-18 | 2020-03-31 | 陶氏环球技术有限责任公司 | 制作弹性体聚烯烃外壳的方法 |
KR20180002810A (ko) * | 2015-05-06 | 2018-01-08 | 바스프 에스이 | 복합 재료 제조 방법 |
US9738812B2 (en) | 2015-08-24 | 2017-08-22 | Red Spot Paint & Varnish Co., Inc. | Cationic-stabilized dispersions, hybridized cationic-stabilized dispersions, in-mold coated articles prepared utilizing such stabilized dispersions, and methods for manufacturing same |
WO2018017701A1 (en) | 2016-07-19 | 2018-01-25 | Cummins Filtration Ip, Inc. | Perforated layer coalescer |
US20190030876A1 (en) * | 2017-07-31 | 2019-01-31 | GM Global Technology Operations LLC | Method and system for using an open pour spray urethane process with a single tool for trim components |
CN108467472B (zh) * | 2018-04-01 | 2021-02-09 | 黎明化工研究设计院有限责任公司 | 一种无溶剂聚氨酯树脂及其在高剥离强度水性/无溶剂聚氨酯合成革中的应用 |
US11104822B2 (en) | 2018-04-18 | 2021-08-31 | Covestro Llc | Processes for In-Mold coating systems for molding, and products formed therefrom |
WO2020161110A1 (de) * | 2019-02-05 | 2020-08-13 | Basf Polyurethanes Gmbh | In-mould coating für zwischensohlen aus cellasto |
US20210094207A1 (en) * | 2019-10-01 | 2021-04-01 | GM Global Technology Operations LLC | Interior trim panel for a vehicle and method of forming an interior trim panel for a vehicle |
US11618188B2 (en) | 2020-12-02 | 2023-04-04 | Global Ip Holdings, Llc | Automated manufacturing method and system and in-mold coated plastic article produced thereby |
US11518072B2 (en) | 2020-12-02 | 2022-12-06 | Global Ip Holdings, Llc | Automated manufacturing method and system and in-mold coated plastic article produced thereby |
Family Cites Families (45)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1889905A (en) | 1930-02-17 | 1932-12-06 | Jr Charles Marshall Saeger | Core or mold binder, coating or paste |
SU383608A1 (ru) | 1971-10-19 | 1973-05-23 | Антиадгезионный разделительный состав | |
US4195148A (en) | 1978-07-12 | 1980-03-25 | Uniroyal, Inc. | Polyurethane spray composition containing lactone viscosity modifier |
JPS5525367A (en) | 1978-08-11 | 1980-02-23 | Toyo Tire & Rubber Co Ltd | Method of fabricating polyurethane molded product with skin |
US4285897A (en) | 1979-01-11 | 1981-08-25 | Nalco Chemical Company | Water-based anti-blemish paint |
DE2916700A1 (de) | 1979-04-25 | 1980-10-30 | Metzeler Kautschuk | Trennmittel zum ausformen von kunststoffen, insbesondere polyurethan-kunststoffen |
US4350777A (en) | 1980-03-28 | 1982-09-21 | Bayer Aktiengesellschaft | Impermeable molded articles of cellular polyurethane elastomers produced with organofunctional polysiloxane-derivatives and their use as spring elements |
DE3014161A1 (de) | 1980-04-12 | 1981-10-22 | Basf Ag, 6700 Ludwigshafen | Verfahren zur herstellung von polyurethan-formkoerpern |
US4356230A (en) | 1980-07-10 | 1982-10-26 | International Telephone And Telegraph Corporation | Molded plastic product having a plastic substrate containing a filler and an in-mold plastic coating firmly bonded thereon and a process for its manufacture |
UST100701I4 (en) | 1980-09-17 | 1981-06-02 | Ici Americas Inc. | In-mold coating compositions containing non-functional liquid copolymers and free isocyanate containing compounds |
JPS57178814A (en) | 1981-04-30 | 1982-11-04 | Kuraray Co Ltd | Manufacture of molded resin molding and mold therefor |
US4520042A (en) | 1983-06-20 | 1985-05-28 | Thermocell Development, Ltd. | High-modulus, flexible urethane coating and method of preparation |
US4668460A (en) | 1985-04-02 | 1987-05-26 | The Sherwin-Williams Company | Method of molding and coating a substrate in a mold. |
LU86007A1 (fr) | 1985-07-15 | 1987-02-04 | Prb Sa | Procede de preparation,par pistolage,d'une couche faconnee |
US5207961A (en) | 1986-06-06 | 1993-05-04 | Bayer Aktiengesellschaft | Injection-moulded article and process for the production thereof |
GB8616034D0 (en) | 1986-07-01 | 1986-08-06 | Merris Dev Engineers Ltd | Vibratory mixers |
DE3624427A1 (de) | 1986-07-18 | 1988-01-21 | Stankiewicz Alois Dr Gmbh | Adhaesives zerstoerungsfrei entfernbares isolationssystem |
DE3643821A1 (de) * | 1986-11-05 | 1988-05-19 | Kloeckner Ferromatik Desma | Formenstationen, insbesondere fuer rundtischanlagen, zum anformen von schuhsohlen mit einer laufsohle aus elastomer und einer zwischensohle aus einem zu polyurethan ausreagierendem gemisch aus isocyanat und polyol an schuhschaefte |
BE1000767A7 (nl) | 1987-07-16 | 1989-03-28 | Recticel | Werkwijze en inrichting voor het vormen van een laag polyurethaan op een oppervlak door spuiten. |
DE3809524A1 (de) | 1988-03-22 | 1989-10-05 | Bayer Ag | Verfahren zur herstellung von verbundkoerpern und die nach diesem verfahren erhaeltlichen verbundkoerper |
JPH01240577A (ja) | 1988-03-22 | 1989-09-26 | Tanabe Kagaku Kogyo Kk | ポリウレタン成形物用モールドコート塗料 |
DE3820704A1 (de) | 1988-06-18 | 1989-12-21 | Basf Ag | Mit einer konturierten, mehrschichtigen folie versehene polyurethan-formkoerper, verfahren zu ihrer herstellung und ihre verwendung |
US5130402A (en) | 1988-07-01 | 1992-07-14 | Sanyo Chemical Industries, Ltd. | Coating composition and plastisol composition, and articles coated therewith |
BE1002762A7 (nl) | 1989-01-20 | 1991-05-28 | Recticel | Werkwijze voor het bereiden en toepassen van verspuitbaar lichtstabiel polyurethaan. |
BE1002899A6 (nl) | 1989-03-03 | 1991-07-16 | Recticel | Werkwijze voor het vervaardigen van voorwerpen met een elastomeren buitenwand en een kunststofschuim kern. |
US4985490A (en) | 1989-04-12 | 1991-01-15 | Bayer Aktiengesellschaft | Method of direct manufacture of pigmented polyurethane powder |
EP0425240A3 (en) * | 1989-10-25 | 1992-03-04 | Bridgestone Australia Ltd., | Moulded panel |
IT1246263B (it) | 1990-09-07 | 1994-11-17 | Montedipe Srl | Procedimento per la preparazione di corpi formati con pelle integrata in poliuretano e corpi formati cosi' ottenuti. |
US5082609A (en) | 1990-10-22 | 1992-01-21 | Bridgestone Australia Ltd. | Method of forming a moulded panel |
US5284918A (en) | 1991-05-01 | 1994-02-08 | W. R. Grace & Co.-Conn. | One package polyurethane/thermoplast plastisol composition |
JP2999577B2 (ja) | 1991-06-07 | 2000-01-17 | サンスター技研株式会社 | ポリ塩化ビニルプラスチゾル系シーラー組成物 |
US5362819A (en) | 1992-01-30 | 1994-11-08 | Gencorp Inc. | Polyester-flexible polymer block copolymers and mixtures thereof |
BE1005821A3 (nl) | 1992-05-18 | 1994-02-08 | Recticel | Werkwijze voor het vervaardigen van zelfdragende kunststof garnituuronderdelen en aldus vervaardigd garnituuronderdeel. |
US5387390A (en) | 1993-04-26 | 1995-02-07 | Atoma International Inc. | Method of molding a vehicle door panel with a soft arm rest |
US5397409A (en) | 1993-04-26 | 1995-03-14 | Atoma International, Inc. | Method for molding a vehicle door panel |
US5387750A (en) | 1993-08-27 | 1995-02-07 | The Sherwin-Williams Company | Two-component urethane in-mold coating composition |
IT1272723B (it) | 1993-10-15 | 1997-06-26 | Nutek Srl | Procedimento per la integrazione fra pelle conciata e film di poliuretano |
US6071619A (en) | 1994-06-01 | 2000-06-06 | Recticel | Method and spray mould assembly for manufacturing an elastomeric skin of at least two elastomeric materials and such elastomeric skin |
JPH0871177A (ja) | 1994-09-09 | 1996-03-19 | Sumitomo Rubber Ind Ltd | 塗装ゴルフボール |
US5580501A (en) | 1994-11-07 | 1996-12-03 | Gallagher; Michael J. | Method of manufacturing an interior trim panel using polyurethane powder |
US5595701A (en) * | 1995-05-12 | 1997-01-21 | The Goodyear Tire & Rubber Company | Process for making a polyurea backed product with a polyurethane skin |
JPH09315115A (ja) * | 1996-05-27 | 1997-12-09 | Bridgestone Corp | タイヤ滑り止め具 |
US5885662A (en) * | 1997-01-31 | 1999-03-23 | Atoma International, Inc. | Decorative automotive interior trim articles with integral light stable polyurethane elastomer covering and process for making the same |
AU744634B2 (en) * | 1997-04-18 | 2002-02-28 | Magna Seating Inc. | Decorative automotive interior trim articles with cast integral light stable covering and process for making the same |
BR9810131A (pt) * | 1997-06-16 | 2000-08-08 | Magna Interior Systens Inc | Processo para fabricar uma estrutura semelhante a um painel, e, artigo |
-
1999
- 1999-05-21 US US09/316,149 patent/US6544449B1/en not_active Expired - Lifetime
- 1999-05-21 JP JP2000550654A patent/JP2002516194A/ja active Pending
- 1999-05-21 AU AU38055/99A patent/AU763172B2/en not_active Ceased
- 1999-05-21 EP EP99920485A patent/EP1079962B1/de not_active Expired - Lifetime
- 1999-05-21 CA CA002321707A patent/CA2321707A1/en not_active Abandoned
- 1999-05-21 WO PCT/CA1999/000424 patent/WO1999061216A1/en not_active Application Discontinuation
- 1999-05-21 CN CN99805534A patent/CN1120080C/zh not_active Expired - Fee Related
- 1999-05-21 DE DE69914322T patent/DE69914322T2/de not_active Expired - Lifetime
- 1999-05-21 AT AT99920485T patent/ATE258108T1/de not_active IP Right Cessation
- 1999-05-21 BR BR9910600-0A patent/BR9910600A/pt not_active Application Discontinuation
- 1999-05-21 KR KR1020007012210A patent/KR20010043259A/ko not_active Application Discontinuation
Non-Patent Citations (1)
Title |
---|
See references of WO9961216A1 * |
Also Published As
Publication number | Publication date |
---|---|
CN1120080C (zh) | 2003-09-03 |
CA2321707A1 (en) | 1999-12-02 |
JP2002516194A (ja) | 2002-06-04 |
DE69914322D1 (de) | 2004-02-26 |
ATE258108T1 (de) | 2004-02-15 |
US6544449B1 (en) | 2003-04-08 |
BR9910600A (pt) | 2001-01-16 |
AU3805599A (en) | 1999-12-13 |
DE69914322T2 (de) | 2004-11-25 |
EP1079962B1 (de) | 2004-01-21 |
AU763172B2 (en) | 2003-07-17 |
WO1999061216A1 (en) | 1999-12-02 |
CN1302250A (zh) | 2001-07-04 |
KR20010043259A (ko) | 2001-05-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1079962B1 (de) | Dekorinnenteile für autos mit in der form beschichteter, integrierter elastomerabdeckung aus aromatischem polyurethan und verfahren zur herstellung derselben | |
EP0963283B1 (de) | Verfahren zum herstellen von dekorativen kraftfahrzeuginnenverkleidungen mit vollständiger und lichtstabiler polyurethanelastomerbeschichtung | |
EP0977657B1 (de) | Dekorationsinnenbekleidigungselemente für kraftfahrzeuge mit einer gegossenen, lichtstabilen bedeckung und verfahren zu deren herstellung | |
US20040126532A1 (en) | Trim articles with light stable covering containing invisible tear seam, and process of making the same | |
MXPA00010412A (en) | Decorative automotive interior trim articles with integral in-mold coated polyurethane aromatic elastomer covering and process for making the same | |
EP1113914B1 (de) | Verkleidungsgegenstände mit lichtstabilen abdeckungen versehen mit unsichtbaren aufreisslinien und verfahren zu deren herstellung | |
WO2000076753A1 (en) | Process of making decorative automotive interior trim articles with integrated components | |
MXPA99007059A (en) | Process for making decorative automotive interior trim articles with integral light stable polyurethane elastomer covering | |
CZ261699A3 (cs) | Způsob výroby výrobků pro dekoraci vnitřku automobilu s povrchovou vrstvou z integrálního lehkého stabilního polyuretanového elastomeru |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20001216 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT DE ES FR GB IT PT SE |
|
17Q | First examination report despatched |
Effective date: 20021119 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT DE ES FR GB IT PT SE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED. Effective date: 20040121 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20040121 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REF | Corresponds to: |
Ref document number: 69914322 Country of ref document: DE Date of ref document: 20040226 Kind code of ref document: P |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20040421 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20040502 |
|
ET | Fr: translation filed | ||
PLBI | Opposition filed |
Free format text: ORIGINAL CODE: 0009260 |
|
PLBQ | Unpublished change to opponent data |
Free format text: ORIGINAL CODE: EPIDOS OPPO |
|
PLAX | Notice of opposition and request to file observation + time limit sent |
Free format text: ORIGINAL CODE: EPIDOSNOBS2 |
|
26 | Opposition filed |
Opponent name: RECTICEL Effective date: 20041020 |
|
PLAX | Notice of opposition and request to file observation + time limit sent |
Free format text: ORIGINAL CODE: EPIDOSNOBS2 |
|
PLAX | Notice of opposition and request to file observation + time limit sent |
Free format text: ORIGINAL CODE: EPIDOSNOBS2 |
|
PLBB | Reply of patent proprietor to notice(s) of opposition received |
Free format text: ORIGINAL CODE: EPIDOSNOBS3 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20060522 Year of fee payment: 8 |
|
PLCK | Communication despatched that opposition was rejected |
Free format text: ORIGINAL CODE: EPIDOSNREJ1 |
|
PLBN | Opposition rejected |
Free format text: ORIGINAL CODE: 0009273 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: OPPOSITION REJECTED |
|
27O | Opposition rejected |
Effective date: 20070517 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20040621 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20080131 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20070531 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20150512 Year of fee payment: 17 Ref country code: GB Payment date: 20150520 Year of fee payment: 17 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 69914322 Country of ref document: DE |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20160521 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20161201 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160521 |